CN115160521A - Triazine-based porous polymer @ CNT composite material and preparation method and application thereof - Google Patents
Triazine-based porous polymer @ CNT composite material and preparation method and application thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 239000007772 electrode material Substances 0.000 description 6
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
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Abstract
The invention provides a triazine-based porous polymer @ CNT composite material as well as a preparation method and application thereof, and belongs to the technical field of organic polymer-based composite materials. The composite material is prepared by reacting 4,4'- (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine with a nitrogen heterocyclic structure as a basic skeleton and 4,4' -biphenyl dicarboxaldehyde through Schiff base to prepare a triazine-based porous skeleton, and adding CNT in the reaction process to prepare the triazine-based porous polymer @ CNT composite material. Book (I)The composite material can be used as a battery cathode material to be applied to a lithium ion battery, has good activity and stability, and is 1A g ‑1 Can still provide 350.9mAh g after circulating for 2000 circles under high current density ‑1 The specific capacity of (a).
Description
Technical Field
The invention belongs to the technical field of organic polymer-based composite materials, and particularly relates to a triazine-based porous polymer @ CNT composite material as well as a preparation method and application thereof.
Background
Driven by different energy and environmental issues and the large consumption of non-renewable fossil fuels, rechargeable Lithium Ion Batteries (LIBs) with higher energy density and stable cycling performance have become the most popular energy storage devices at present. However, the development of materials with renewable, environmentally friendly electrodes is a key issue for the sustainable development of LIBs. Recent studies have shown that organic electrode materials are one of the best candidates for energy storage device research due to their diversity, environmental friendliness, and structural designability. Based on this, researchers have designed sustainable electrode materials such as organic radicals, conjugated carbonyl compounds, organic sulfur and organic carbon/nitrogen compounds that can be used in energy storage devices.
In recent years, the use of nitrogen-containing compounds (OCNs) as electrode materials has been reported in large numbers. The electrochemical active site containing N element can play the role of an electrochemical reaction center and has the following advantages: compared with other materials, the OCN can provide more lithium storage sites per active cell; OCN can provide high conductivity due to its high nitrogen content; the heteroaromatic N atom of the OCN may increase the redox potential. However, the solubility, thermochemical instability and poor conductivity of such organic small molecule electrode materials are serious obstacles limiting their development in energy storage systems. Therefore, the design of a stable polymer skeleton structure with an electroactive group as a high-performance negative electrode material of a lithium ion battery through molecular engineering is very important.
The nitrogen-containing porous organic polymer is a rapidly developed porous polymer material, and has become a thermoelectric material in the field of energy storage by virtue of low skeleton density, environmental friendliness, high thermochemical stability in a severe environment and molecular structure diversity. Especially, the electrophilic triazine ring is introduced into a polymer skeleton, so that the energy level and the energy gap of a molecular orbit can be effectively adjusted, and the electron transport capacity and the oxidation-reduction potential can be further adjusted. However, due to the close packing between polymers, li is caused even at high current densities + It is also difficult to penetrate into deep buried layerIn the internal active site in between. This inevitably results in an under-utilization of the redox active sites, thereby reducing the lithium storage capacity of the electrode material.
Disclosure of Invention
The invention aims to provide a triazine-based porous polymer @ CNT composite material, and a preparation method and application thereof.
The invention adopts the following technical scheme:
the invention firstly provides a triazine-based porous polymer @ CNT composite material, which is formed by adding CNT in the process of synthesizing the triazine-based porous polymer, wherein the structural formula of the triazine-based porous polymer TAPT-BTPA is shown as a formula 1:
the invention also provides a preparation method of the triazine-based porous polymer @ CNT composite material, which comprises the following steps:
adding 4,4'- (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, 4' -biphenyl dicarboxaldehyde and CNT into a reaction vessel, adding a solvent for dissolving, then adding glacial acetic acid to obtain a mixture, and placing the mixture into a mixer for reacting to obtain the triazine-based porous polymer @ CNT composite material.
Preferably, the mass ratio of the 4,4'- (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, 4' -biphenyldicarbaldehyde and CNT is 14.17: 13.50.
preferably, the solvent is acetonitrile.
Preferably, the concentration of the glacial acetic acid is 6M.
Preferably, the reaction temperature is room temperature, and the reaction time is 96h.
The invention also provides application of the triazine-based porous polymer @ CNT composite material as a negative electrode material in a lithium ion battery.
The invention has the advantages of
The invention provides a triazine-based porous polymer @ CNT composite material and a preparation method and application thereof, wherein the composite material is prepared by taking 4,4'- (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine (TAPT) with a nitrogen-containing heterocyclic structure as a basic skeleton to react with 4,4' -biphenyl dicarboxaldehyde (BTPA) through Schiff base, and CNT is added in the reaction process to prepare the triazine-based porous polymer @ CNT composite material. Wherein, the synthesized TAPT-BTPA @ CNT has a stable polymer skeleton structure, solves the problem that organic small molecules are easy to dissolve in electrolyte, and rich triazine skeleton and imine bond in the triazine-based porous polymer can be used as Li + The insertion sites of (a), increasing the capacity of LIBs; BTPA is selected as a monomer, so that the pore diameter of the polymer can be increased, and Li is facilitated + Diffusion of (2); TAPT is selected as a monomer, electrophilic triazine ring is introduced into the polymer, so that the energy level and band gap of a molecular orbit can be effectively adjusted, and the electron transmission capability and the oxidation-reduction potential can be further adjusted. The CNT is introduced to enable the polymer to be separated in situ in the growth process, the polymer only forms a few layers of polymers around the CNT through pi-pi interaction, and the serious stacking phenomenon of the polymer is effectively solved. The polymer grows on the CNT in a controllable way, so that the conductivity of the composite material can be improved, and the utilization rate of active sites of the polymer can be further improved. In view of the improved conductivity, porous structure and abundant active sites of the composite material, the composite material exhibits better energy storage performance as a LIBs cathode material. Can be used for lithium ion battery, has good activity and stability at 1 Ag -1 Can still provide 350.9mAh g after circulating 2000 circles under high current density -1 The specific capacity of (a).
Drawings
FIG. 1 is a FT-IR spectrum of TAPT, BTPA, TAPT-BTPA of comparative example 1 and TAPT-BTPA @ CNT produced in example 1.
FIG. 2 is an SEM photograph of TAPT-BTPA of comparative example 1;
FIG. 3 is an SEM photograph of TAPT-BTPA @ CNT obtained by the preparation of example 1;
FIG. 4 is a thermogravimetric plot of TAPT-BTPA of comparative example 1 and TAPT-BTPA @ CNT prepared in example 1;
FIG. 5 is a photograph of TAPT-BTPA of comparative example 1 and TAPT-BTPA @ CNT prepared in example 1 in an electrolyte;
FIG. 6 is the N of TAPT-BTPA of comparative example 1 and TAPT-BTPA @ CNT prepared in example 1 2 Adsorption-desorption isotherm curves;
FIG. 7 shows TAPT-BTPA @ CNT prepared in example 1 at 0.1mV s -1 A CV curve of (a);
FIG. 8 shows TAPT-BTPA @ CNT obtained in example 1 at 1A g -1 The current density of (a);
FIG. 9 is a graph of the rate performance of TAPT-BTPA @ CNT prepared in example 1;
FIG. 10 is an EIS profile of TAPT-BTPA @ CNT prepared in example 1 in the initial state and after 1, 5, 50, 100 and 200 cycles.
Detailed Description
The invention firstly provides a triazine-based porous polymer @ CNT composite material, which is formed by adding CNT in the process of synthesizing a triazine-based porous polymer, wherein the structural formula of the triazine-based porous polymer TAPT-BTPA is shown as a formula 1:
the invention also provides a preparation method of the triazine-based porous polymer @ CNT composite material, which comprises the following steps:
adding 4,4'- (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, 4' -biphenyl dicarboxaldehyde and CNT into a reaction vessel, adding a solvent for dissolving, wherein the dissolving mode is ultrasonic dissolving, the ultrasonic time is 1-2min, the solvent is acetonitrile, glacial acetic acid is added, the concentration of the glacial acetic acid is 6M, obtaining a mixture, placing the mixture into a mixer, shaking vigorously for 10-15s, reacting, the reaction temperature is room temperature, the reaction time is 96h, collecting the obtained product by centrifugation, washing the product by N, N-dimethylformamide, tetrahydrofuran and absolute ethyl alcohol for three times, and finally drying the powder under high vacuum condition, wherein the drying time is 24-48h, and obtaining the triazine-based porous polymer @ CNT composite material.
According to the present invention, the mass ratio of 4,4',4"- (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, 4' -biphenyldicarboxaldehyde and CNT is preferably 14.17: 13.50.
the invention also provides application of the triazine-based porous polymer @ CNT composite material as a negative electrode material in a lithium ion battery.
The present invention is described in further detail below with reference to specific examples, in which the starting materials are all commercially available.
Comparative example 1 Synthesis of triazine-based porous Polymer (TAPT-BTPA)
4,4'- (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine (14.17 mg) and 4,4' -biphenyldicarbaldehyde (12.62 mg) were added to the test tube. Then 5mL of acetonitrile was added and sonicated for 1min to allow complete dissolution. Thereafter, 0.4mL of 6M glacial acetic acid was added. Subsequently, the mixture was shaken vigorously on a vortex mixer for 10s and reacted at room temperature for 96h. The resulting yellow precipitate was collected by centrifugation and washed three times with N, N-dimethylformamide, tetrahydrofuran and absolute ethanol, respectively. Finally, the powder was dried under high vacuum for 24h to give 13.5mg of a yellow solid powder. The reaction process is as follows:
example 1
4,4'- (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine (14.17 mg), 4' -biphenyldicarbaldehyde (12.62 mg) and CNT (13.50 mg) were added to a test tube. Then 5mL of acetonitrile was added and sonicated for 1min to allow complete dissolution. Thereafter, 0.4mL of 6M glacial acetic acid was added. Subsequently, the mixture was shaken vigorously on a vortex mixer for 10s and reacted at room temperature for 96h. The resulting yellow precipitate was collected by centrifugation and washed three times with N, N-dimethylformamide, tetrahydrofuran and absolute ethanol, respectively. Finally, the powder was dried under high vacuum for 24h to give a triazine based porous polymer @ CNT composite.
FIG. 1 is a FT-IR spectrum of TAPT, BTPA, TAPT-BTPA of comparative example 1 and TAPT-BTPA @ CNT produced in example 1. As can be seen from FIG. 1, 1625cm appeared in the FTIR spectra of TAPT-BTPA and TAPT-BTPA @ CNT -1 Strong C = N stretching peak, meanwhile, 2794, and 2701cm -1 The peaks at 3466, 3333 and 3219cm which are characteristic of-CH in BTPA -1 Almost disappearance of characteristic peak belonging to-NH-stretching vibration in TAPT, and 1605cm -1 The disappearance of-C = O in BTPA indicates the success of the condensation reaction between TAPT and BTPA. The presence of the weaker amino characteristic peak in the spectrum of TAPT-BTPA is attributed to the unreacted side chain groups. FTIR spectrum of TAPT-BTPA @ CNT at 3402cm -1 The broad characteristic peak at (a) is due to the presence of part of the water in the material.
FIG. 2 is an SEM photograph of TAPT-BTPA of comparative example 1; as can be seen from FIG. 2, TAPT-BTPA exhibits a coral-like nano-rod morphology with a smooth surface and a uniform morphology.
FIG. 3 is an SEM photograph of TAPT-BTPA @ CNT obtained by the preparation of example 1; as can be seen from FIG. 3, after doping CNT, coral-like morphology disappeared, TAPT-BTPA @ CNT appeared linear uniform nanotube morphology, and no large block-like separate polymer existed around the tube, indicating that it was uniformly grown on the surface of CNT in the form of thin layer. And the composite material becomes fluffy and has a large number of pores after the CNT and the polymer are compounded, which is beneficial to the entering of electrolyte and the transmission of electrons, thereby hopefully improving the performances of the two polymers in the aspect of electrochemical energy storage.
FIG. 4 is a thermogravimetric plot of TAPT-BTPA of comparative example 1 and TAPT-BTPA @ CNT prepared in example 1; as can be seen from FIG. 4, TAPT-BTPA has a 4.85% capacity loss at 200 deg.C due to the presence of organic solvents and moisture in the material. TAPT-BTPA has no obvious capacity loss before 500 ℃, has 89.52% of weight retention rate, has rapid weight reduction due to partial skeleton collapse after 500 ℃, and still has 50.78% of weight retention rate at 700 ℃. After being compounded with CNT, TAPT-BTPA @ CNT also has good weight retention rate before 500 ℃, and still maintains weight retention rate of about 82.76% at the temperature of 700 ℃, which indicates that the polymer has better skeleton stability.
FIG. 5 is a photograph of TAPT-BTPA of comparative example 1 and TAPT-BTPA @ CNT prepared in example 1 in an electrolyte of 1M LiPF 6 Dissolved in ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate (volume ratio 1. As can be seen from FIG. 5, TAPT-BTPA and TAPT-BTPA @ CNT maintain good forms in the electrolyte, and the electrolyte is clear and transparent, so that the good structural stability of the electrolyte is further proved, and the reversible redox reaction of the electrolyte in the electrochemical energy storage process is expected to be realized.
FIG. 6 is the N of TAPT-BTPA of comparative example 1 and TAPT-BTPA @ CNT prepared in example 1 2 Adsorption-desorption isotherm curves; as can be seen from FIG. 6, for TAPT-BTPA, the specific surface area was determined to be 32.46m 2 g -1 . While the BET of TAPT-BTPA @ CNT was determined to be 209.98m 2 g -1 . It is clear that the specific surface area of the polymer increases significantly after recombination with the CNTs, providing good conditions for rapid diffusion and penetration of the electrolyte into the interior of the material. And it can be seen that the isotherms of TAPT-BTPA and TAPT-BTPA @ CNT show a rapid rise at a relatively high relative pressure (0.8-1), indicating that they are both mesoporous.
TAPT-BTPA @ CNT is used as a negative electrode material and assembled into a CR2032 coin cell according to the technology in the field, so that the lithium storage performance of the TAPT-BTPA @ CNT used as the negative electrode material is researched. The specific steps of the battery assembly are as follows: TAPT-btpa @ cnt, acetylene black and sodium carboxymethylcellulose were mixed in a weight ratio of 8. The slurry was thoroughly ground in a mortar for 60 minutes. The homogeneous slurry was then coated on a copper foil and dried at room temperature. And cutting the dried electrode plate into a 1cm round piece. And assembling the CR2032 button cell in the glove box filled with Ar according to the sequence of the negative electrode shell, the electrode plate, the electrolyte, the diaphragm, the lithium plate, the gasket, the elastic sheet and the positive electrode shell. First, its redox mechanism was investigated by CV test.
FIG. 7 shows TAPT-BTPA @ CNT prepared in example 1 at 0.1mV s -1 A CV curve of (a); as can be seen from FIG. 7, the CV curveSignificant reduction peaks can be found only at 1.81v,0.93v and 0.66V in the first turn, which is caused by the formation of the SEI film. In subsequent cycles, the broader weak reduction peaks at 1.22-0.58V correspond to lithiation of the C = C double bond and the C = C double bond. During the subsequent oxidation process, the broader weak oxidation peak at 0.68-1.44V is due to the intercalation of lithium ions and the C = C double bond and C = C double bond reformation. The CV curves exhibited an overlapping phenomenon during subsequent cycles, demonstrating the stable redox reaction of TAPT-BTPA @ CNT.
FIG. 8 shows TAPT-BTPA @ CNT obtained in example 1 at 1A g -1 The current density of (a); FIG. 8 shows that, in the first turn, the specific reversible charge capacity of TAPT-BTPA @ CNT is 572.8mAh g -1 The lower coulombic efficiency at this time was due to the formation of the SEI film, and during the subsequent constant current circulation, the coulombic efficiency gradually increased to 98%, and the first 30 cycles showed a faster decay of the capacity, which may be caused by decomposition of the electrolyte at a large current density. The capacity tends to increase later in the circulation due to the activation of more active sites, remains stable by around 350 cycles, and can still provide 350.9mAh g after 2000 cycles -1 The charging specific capacity and the coulombic efficiency of the material reach 99 percent, which shows that the TAPT-BTPA @ CNT is used as a negative electrode material and has better energy storage performance.
In addition, in order to further evaluate the potential application of TAPT-BTPA @ CNT as the negative electrode material, the rate performance under the stepped current density is also evaluated through continuous constant current charge and discharge tests, which is an important index for realizing rapid charge and discharge of the electrode material. FIG. 9 is a graph of the rate performance of TAPT-BTPA @ CNT prepared in example 1; as can be seen from FIG. 9, at 0.1 Ag -1 After 10 cycles of the lower cycle, when the current density is from 0.2 ag -1 Increase in a step-like manner to 5 ag -1 TAPT-BTPA @ CNT provides 490.9mAh g capacity at different current densities -1 、382.4mAh g -1 、303.4mAh g -1 、243.6mAh g -1 And 177.9 mAh g -1 When the current density is readjusted back to 0.1 ag -1 Still, 515.3mAh g can be provided -1 Syndrome of adverse volume of qiThe better rate capability is realized.
FIG. 10 is an EIS profile of TAPT-BTPA @ CNT prepared in example 1 in the initial state and after 1, 5, 50, 100 and 200 cycles. As can be seen in fig. 10, the initial EIS maps are shown without cycling and after cycles 1, 5, 50, 100, 200. Wherein, the map is mainly divided into two parts: a low band slope line and a high band half circle, representing the varburg resistance (Rw) and the charge transfer resistance (Rct), respectively. It was found that the value of Rct increased after 1 cycle of TAPT-BTPA @ CNT, due to the formation of SEI film in the first cycle; rct gradually decreased after 5 cycles, which is caused by the electrochemical activation phenomenon; approximate Rct values after 50, 100 cycles and even up to 200 cycles confirm the structural stability of TAPT-btpa @ cnt in repeated redox processes.
Claims (7)
1. The triazine-based porous polymer @ CNT composite material is characterized in that the composite material is formed by adding CNT in the process of synthesizing a triazine-based porous polymer, and the structural formula of the triazine-based porous polymer TAPT-BTPA is shown as a formula 1:
2. the method of claim 1, wherein the method comprises:
adding 4,4'- (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, 4' -biphenyl dicarboxaldehyde and CNT into a reaction vessel, adding a solvent for dissolution, then adding glacial acetic acid to obtain a mixture, and placing the mixture into a mixer for reaction to obtain the triazine-based porous polymer @ CNT composite material.
3. The method for preparing the triazine-based porous polymer @ CNT composite material as claimed in claim 2, wherein the mass ratio of 4,4'- (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, 4' -biphenyldicarboxaldehyde and CNT is 14.17: 13.50.
4. the method of claim 2, wherein said solvent is acetonitrile.
5. The method of claim 2, wherein glacial acetic acid is present at a concentration of 6M.
6. The preparation method of the triazine-based porous polymer @ CNT composite material as claimed in claim 2, wherein the reaction temperature is room temperature, and the reaction time is 96 hours.
7. The use of the triazine-based porous polymer @ CNT composite of claim 1 as a negative electrode material in a lithium ion battery.
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